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Electronic structure and photoelectron spectra of bispentalene complexes of thorium and uranium
journal contribution
posted on 2023-06-08, 00:24 authored by Geoff Cloke, JC Green, CN JardineThe preparation of [U{¿8-C8H4(1,4-SiiPr 3)2}2] is reported. The binding of the pentalene ligand in an ¿8 mode is examined by density functional calculations and photoelectron spectroscopy. Geometry optimization of [M(¿8-C8H6)2], M = Th with D2d and D2 symmetry constraints, gives structures in good agreement with the X-ray structure found for [Th{¿8-C8H4(1,4-SiiPr 3)2}2); in particular the folded nature of the ligand is well reproduced by the calculation. Examination of the barrier to relative rotation of the two ligands only showed a significant energy rise when the two rings were eclipsed. Geometry optimization for M = U, assuming D2d symmetry and a triplet state, gave a structure similar to the Th compound but with shorter metal-carbon bond lengths. The two U f electrons were constrained to occupy degenerate orbitals of e symmetry. He I and He II spectra of [M{¿8-C8H4(1,4-SiiPr 3)2}2], M = Th and U, are presented and assigned with the aid of density functional calculations. The principal binding is by d bonds between the upper occupied p orbitals of the pentalene dianion and the actinide d and f orbitals of appropriate symmetry.
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Publication status
- Published
Journal
OrganometallicsISSN
02767333Issue
6Volume
18Department affiliated with
- Chemistry Publications
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- No
Peer reviewed?
- Yes
Legacy Posted Date
2012-02-06Usage metrics
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